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I've driven all over Provence and the Languedoc in more than 100 trips and never encountered any road I would call "hair-raising" except maybe the one near the Gorges du Tarn that was clearly marked on the Michelin map as "dangerous," and even that was good for a good laugh. And I'm a skittish driver. The French are fabulous engineers. They don't construct dangerous roadways. Michelin maps show clearly which roads may give you pause, but even those aren't bad, just bumpy and narrow.

I'd avoid the Gorges de Galamus if you don't like hair-raising. Or drive it from St Paul up not down to St Paul, so you have the gorge wall next to you not the Gorges itself, which is perhaps less scary.
If you are up to it though I can recommend it.

There are a few hair-raising roads around that area, but you have to go out of your way to find them.

Well, there's one between Limoux and Collioure that wasn't a walk in the park, in fact, I wish I could have walked as it wasn't very long, thankfully. The road wound along the side of a gorge, mostly one lane with pull-overs every so often so cars can pass. My atlas is in the car so I'll post the route number tomorrow. It was a stunning drive, or so my passengers said.

I guess everyone has a different threshold but I didn't find the Gorges de Galamus at all scary, and I was a passenger. There are a couple of roads in and out of the Gorges du Tarn that you probably wouldn't enjoy. Unless you have a real problem with vertigo I'm with St. Cirq in thinking there aren't any hair raising/death defying roads in Provence or Languedoc and I think I've hit all the areas with twisty, hilly roads (except Mt. Ventoux). But if you want to err on the side of caution then heed the advice of those who provide their lists of scary roads. In which case you'd probably want to stay off the small country roads in the Cévennes region.

To me it depends on the kind & height of barrier on the outside road edge. I drove over a hill between Buis-les-Baronnies and Ste-Jallie (east of Nyons/north of Mt Ventoux) which I found scary because the outside road edge barrier was less than knee high. On the other hand I was fine on the Gorges du Tarn, although I had a few flutters on the zigzag into the Gorges du Tarn from Severac-le-Chateau to les-Vignes. I'm also OK if the road edge is heavily treed as opposed to being an open drop.

Grateful for the tip about Gorges de Galamas. Next year I plan to drive all around the southwest from Cahors to Perpignan and would be glad of any advice re scary roads in the area. Also the road down from Mont-de-Marsan to St-Jean-Pied-de-Port and beyond (into Spain) - on Google Earth it looks very forested, which is OK. But is it?

Also (further to my previous posting above), how about the D86 (that's the narrow high inland road, not the coast road) from Collioure to Banyuls-sur-Mer? I've been debating whether to give that a try or not.

The D117 between Foix and Quillan on the way to Perpignan. Don't look down and keep both eyes on the road and both hands on steering wheel. The switchbacks are formidable and you need to really pay attention.

I think this is obviously a matter of opinion or your tolerance for risk, as I imagine there are lots of roads that would make me uncomfortable to drive in Provence (given there have been several already that were). I have drive around Mt Ventoux, also, and I think there was a part of it where I thought I wasn't comfortable and since I was alone, should turn back.

One example, the road leading from the Abbaye de Senanque north to around Venasque is one that is a winding road alongside a mountain in one part and it isn't really very wide. So if you encounter a car coming towards you, and they are a careless driver going down the middle of the road, you could be in big trouble or over the cliff. I think I've encountered other mountain roads that weren't really wide enough for two cars comfortably.

The D117 between Foix and Quillan? Really? Any particular section of it that's bad, or the whole thing? I had that road on my list (a way of getting to Montsegur) and, because it's quite a main road, I hadn't thought to question how scary it might be.

Another I would like feedback on is the D613 from Ax-les-Thermes to Quillan.

I agree re the roads around Senanque & Venasque. I'm so glad otto2 posted this question. I tried to start a similar thread a few of years ago, but it was really hard getting feedback from anyone who understood. Unless one suffers from the fear of high unprotected drops, one cannot appreciate what we're on about. Which is understandable I guess. It's so good (at last) to be hearing opinions from people who seem to know what we're on about!

As I recall when I last drove it, the section between Lavelanet and Quillan is the one where you might want to pay special attention. East of there it becomes relatively smooth all the way to Perpignan with vineyards accompanying you all the way.

The road between Quillan and Foix is good. Ditto for Ax to Quillan. Proof is that there are usually a lot of bikers on these two roads
It is a mountainous area so yes, you should expect winding and curving roads. There are no dangerous roads, but there are dangerous drivers. If you hit the first curve at 90kmph instead of 50, you won't manage the second one. But this applies everywhere, not just in Languedoc or Provence
The Galamus road is one-way during summer with traffic lights at both ends of the Gorge and a long wait if you hit the red light.
Re the D/86 : If you are not used to driving on mountain roads, it would be wise to avoid it. Take the coast road which provides breathtaking views of the coast and the ocean. The D96 is narrow and very winding. The coastal road is not as narrow but still winding

I've driven on lots of mountain roads in Provence that didn't have any guard rails at all, that road north to Venasque doesn't have any guard rail that I can recall. I think that is D177. It wasn't bad on a lot of it (and parts of it aren't that high up), just some sections.

The section of the D117 between Lavelanet and Quillan is 35k. Quite a lot, if you're white-knuckle driving all the way! I'll do what I usually do when I'm considering a potentially scary road: I'll Google-Earth it.

We need to understand that "scary road", "hair raising route" are purely subjective terms. I accept that "there are no dangerous roads" (well, actually, no I don't, but you know what I mean!) and that "there are dangerous drivers", but I think many of the people who have posted here are talking about something personal rather than about any road per se - in my case a personal inability to enjoy heights where there is no protective barrier between me and a vertiginous drop. I know and tell myself the road itself is safe, and I always drive safely on such a road (on any road, actually), but if you suffer from the condition these things do nothing to ease the nerves.

But, returning to the OP's question, we seem to have the beginnings of the list that otto2 asked for:
Gorges du Galamas
Gorges du Verdon (if driving on outside edge)
Gorges du Tarn (maybe?)
Senanque-Venasque
Around Mt Ventoux
A section of the D117 Lavelanet-Quillan
D86 high road Collioure-Baynols-sur-Mer

I definitely agree with the inclusion of the road around the Gorges du Verdon. The buses on this road make it even more hair raising. My husband said never again... in fact, we didn't go all the way around and took a very long way back at the half-way point.

The biggest hair-raising road for me was the road from Barcelonette to the Col d'Allos in the French Alps. Extremely narrow mountain road, limited guard rails, sharp turns, and the possibility of meeting another car. This was far worse than anything we've experienced on Mont Ventoux... we had no idea what we were getting into... we just wanted to travel from Barcelonnette to Colmars and saw this "scenic" road on the Michelin map.

Yep it was Galamus in mid-Sept so no traffic lights and two-way traffic. My main concern was having to back up to let an approaching car pass. We decided to go that way rather than the autoroute to see some of the villages, Rennes les Bains, etc. The scenery was spectacular. I didn't walk down to the chapel, wanted to get to Collioure by late afternoon On the way back, we took the D117 to Foix, which didn't bother me. It's all relative.

You don't need to drive on any of these roads if you want to see the main tourist sites/cities such as Aix en Provence,Arles, Nimes, Avignon, Carcassonne, Sète, Montpellier. It's all easy driving on highways. July and August are very busy months in the south of France in terms of traffic both on highways and country roads.